WO2023244178A1 - Method of recovering electrode material - Google Patents
Method of recovering electrode material Download PDFInfo
- Publication number
- WO2023244178A1 WO2023244178A1 PCT/SG2023/050425 SG2023050425W WO2023244178A1 WO 2023244178 A1 WO2023244178 A1 WO 2023244178A1 SG 2023050425 W SG2023050425 W SG 2023050425W WO 2023244178 A1 WO2023244178 A1 WO 2023244178A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solution
- sulphate
- phosphate
- ions
- chloride
- Prior art date
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 87
- 229910021653 sulphate ion Inorganic materials 0.000 claims abstract description 83
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 69
- 239000003990 capacitor Substances 0.000 claims abstract description 64
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 50
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 47
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 43
- 239000010452 phosphate Substances 0.000 claims abstract description 33
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 48
- 235000021317 phosphate Nutrition 0.000 claims description 45
- -1 sulphate ions Chemical class 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 33
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 6
- 229910052914 metal silicate Inorganic materials 0.000 claims description 6
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 6
- 229910001465 mixed metal phosphate Inorganic materials 0.000 claims description 6
- 229910001482 mixed metal silicate Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 2
- OGCCXYAKZKSSGZ-UHFFFAOYSA-N [Ni]=O.[Mn].[Li] Chemical compound [Ni]=O.[Mn].[Li] OGCCXYAKZKSSGZ-UHFFFAOYSA-N 0.000 claims description 2
- FDLZQPXZHIFURF-UHFFFAOYSA-N [O-2].[Ti+4].[Li+] Chemical compound [O-2].[Ti+4].[Li+] FDLZQPXZHIFURF-UHFFFAOYSA-N 0.000 claims description 2
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 claims description 2
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 claims description 2
- LRVBJNJRKRPPCI-UHFFFAOYSA-K lithium;nickel(2+);phosphate Chemical compound [Li+].[Ni+2].[O-]P([O-])([O-])=O LRVBJNJRKRPPCI-UHFFFAOYSA-K 0.000 claims description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 274
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 238000001069 Raman spectroscopy Methods 0.000 description 30
- 239000012266 salt solution Substances 0.000 description 26
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 25
- 238000001237 Raman spectrum Methods 0.000 description 22
- 238000000926 separation method Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 229910001868 water Inorganic materials 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 19
- 238000004064 recycling Methods 0.000 description 18
- 238000000527 sonication Methods 0.000 description 18
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 15
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 15
- 125000002091 cationic group Chemical group 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 150000001450 anions Chemical class 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 10
- 238000002386 leaching Methods 0.000 description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 8
- 238000013459 approach Methods 0.000 description 8
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 239000007832 Na2SO4 Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 235000010344 sodium nitrate Nutrition 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 229910003202 NH4 Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 230000032798 delamination Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 235000019799 monosodium phosphate Nutrition 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 239000001166 ammonium sulphate Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 231100001261 hazardous Toxicity 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000000794 confocal Raman spectroscopy Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 229910019670 (NH4)H2PO4 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910012223 LiPFe Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
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- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 238000005571 anion exchange chromatography Methods 0.000 description 1
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- 230000005587 bubbling Effects 0.000 description 1
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- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 229910052987 metal hydride Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
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- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure refers to a method of recovering electrode material from a battery or capacitor.
- the present disclosure also relates to electrode material obtained by the method, and a battery or capacitor comprising the electrode material.
- a method of recovering electrode material from a battery or capacitor wherein an electrode of the battery or capacitor is exposed to a solution comprising sulphate, phosphate, nitrate and/or chloride ions.
- the solution in the disclosed method may be non-hazardous and environmentally friendly.
- the solution recovers electrode material from spent batteries and/or capacitors by delaminating/dislodging electrode material from the current collectors without the use of conventional strong acids to leach metal components, and also removes the need for high energy heating processes, such as melting the batteries and/or capacitors.
- the presently disclosed method may also advantageously be performed under ambient conditions which avoid harsh conditions such as highly acidic environments which can result in leaching of metal components and high temperatures to melt the battery or capacitator (smelting), which may require high levels of energy input.
- the presently disclosed method may not require grinding the electrode materials together with the current collectors into fine powders, which reduces the risks of releasing harmful pollutants, dust or fumes into the environment. Without the need for grinding, the disclosed method may also make it easier to separate and extract electrode materials and current collectors.
- the presently disclosed method may also advantageously not release or emit toxic gases or fumes which can pose both health and environmental risks, thereby removing the need for pre-treatment processes before the releasing into the environment.
- the solution may be cost-effective, non-toxic and environmentally friendly, allowing for a safe, sustainable, and scalable solution for large-scale direct recycling of batteries or capacitors.
- the presently disclosed method may comprise a facile and one-step separation of current collectors from electrode material, removing the need for further extraction or post-processing (e.g., leaching or re-calcination with metal precursors) of recovered electrode materials.
- a battery or capacitor comprising the recovered electrode material disclosed herein.
- electrode material obtained by the method disclosed herein.
- the presently disclosed method allows for the recovered electrode material to be directly used as electrode materials for battery/capacitor applications.
- the direct use of the recovered electrode materials may reduce energy consumption as compared to conventional hydrometallurgical and pyrometallurgical methods and may therefore reduce the overall cost of producing new batteries and/or capacitors.
- Recovering and reusing electrode materials may lower the expenses associated with sourcing and processing new raw materials, rendering lower costs and higher affordability for consumers.
- direct recycling and reuse ensures hazardous materials such as heavy metals and toxic chemicals from batteries and capacitors may prevent environmental contamination by reducing the risk of these substances entering ecosystems, groundwater, or air when improperly disposed of.
- direct recycling and reuse of the recovered electrode materials may help create a closed-loop system by reintroducing materials from used batteries or capacitors back into the production cycle. This promotes a circular economy approach, reducing waste and ensuring a sustainable supply of materials for future battery and capacitor production.
- the term "electrode material” refers to a material comprising either anode material, cathode material, or a mixture thereof.
- the electrode material may comprise one or more of metal/mixed metal oxides (cathode material), metal/mixed metal phosphates (cathode material), or metal/mixed metal silicates (cathode material), carbonaceous material (such as carbon, hydrocarbons, graphite) (anode material), or silicon-based materials (anode material).
- the term “delamination” refers to the mechanical separation or detachment of electrode material from the surface of a current collector within an electrochemical system, typically in the context of energy storage devices such as batteries or capacitors. It encompasses the detachment of electrode active materials, binders, and conductive additives from the current collector's substrate. As used herein, the terms “delamination” and “dislodgement” are used interchangeably .
- the term “mixed metal” or “mixed metal material” includes any compound comprising at least two metals.
- the mixed metal material may comprise one or more metals that are present in said batteries/capacitors, such as those present in the electrodes (e.g. cathode and anode materials).
- current collector refers to a substrate for an electrode material able to conduct electrons.
- current collector may comprise metal, metallic or conductive current collectors.
- black mass refers to a composition comprising electrode materials including electrode active materials, polymeric binder, residual current collector material, and other residual particulates.
- the chemical composition of black mass depends upon the chemistry of the battery/capacitor.
- the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
- range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
- Fig. 1 is a schematic diagram of a method of recycling of batteries and/or capacitors using the method disclosed in the present invention to obtain current collector and electrode material.
- the obtained electrode material can be reused in new batteries and/or capacitors.
- Fig. 2 is a schematic diagram showing the use of an integrated sieve system in a method of the present invention.
- Fig. 3 is an image showing the pH values of various sulphate solutions.
- Fig. 4 is a series of Raman spectra of sulphate-based solutions of the present invention.
- Fig. 5a is a series of Raman spectrums of NH4-based sulphates with SDS and without SDS.
- Fig. 5b is a series of Raman spectra of Al-based sulphates with SDS and without SDS.
- Fig. 6 is a Raman spectrum showing the Raman bands of sulphates (X a ) and phosphates (Xb) of solutions of the present invention.
- Fig. 7 is a series of Raman spectra of solutions in Table 2: (a) control solution without sulphates and phosphates (Solution 1); (b) control with sulphates-based solution (Solution 2); (c) control with phosphates-based solution (Solution 3); and (d) control with sulphates- and phosphates-based solution (Solution 7).
- Fig. 8 is a series of graphs of confocal Raman spectrum of rainwater and DI water.
- Fig. 9 is a bar chart showing the concentration of Cl , NO3 and SO4 2 anions in rainwater in parts per million (ppm).
- Fig. 10 is a bar chart showing the concentration of Cl , NO3 and SO4 2 anions in rainwater in parts per million (ppm).
- Fig. 10 are photographs of electrodes after sonication using diluted H2SO4, diluted HNO3, deionized (DI) water, and rainwater (RW).
- Fig. 11 is a series of images of electrodes after sonication at 25 °C for 2 and 5 minutes using DI H2O, rainwater (RW), Li + -based solution, Na + -based solution, NHA-based solution, Mg 2+ -based solution, Zn 2+ -based solution, and Al 3+ -based solution.
- Fig. 12 is an image of two electrodes after sonication using phosphates-based and sulphates-based solutions.
- Fig. 13 is a series of images of electrodes after sonication for 1 minute, 4 minutes, 5 minutes and 10 minutes using different solutions comprising 0.5M sodium dodecyl sulphates (SDS). Images on the right are enlarged images of the electrodes at the respective time intervals and solutions.
- SDS sodium dodecyl sulphates
- Fig. 14 is a series of images of electrodes in the respective solutions (1-7) after sonication at 25°C for 0 minutes, 1 minute, and 15 minutes.
- Fig. 15 is a series of scanning electron microscope (SEM) images of recovered electrode material.
- Fig. 16 is an X-ray diffraction (XRD) pattern of recovered electrode materials.
- Fig. 17 is a schematic diagram of an electrochemical cell configuration using recovered electrode materials as anodes.
- Fig. 18 is a graph showing the galvanostatic charge and discharge curves of recovered electrode materials/lithium (Li) foil at 300 mA g 1 after (i) 1; (ii) 2; (iii) 10; and (iv) 100 cycles.
- Fig. 19 is a graph showing the galvanostatic charge and discharge curves of recovered electrode materials/lithium (Li) foil at 300 mA g 1 after (i) 1; (ii) 2; (iii) 10; and (iv) 100 cycles.
- Fig. 19 is a graph showing the galvanostatic charge and discharge curves of recovered electrode materials/lithium (Li) foil at 300 mA g 1 after (i) 1; (ii) 2; (iii) 10; and (iv) 100 cycles.
- Fig. 19 is a graph showing the galvanostatic charge and discharge curves of recovered electrode materials/lithium (Li) foil at 300 mA g 1 after (i) 1; (ii) 2
- Fig. 19 is a graph showing the (i) charge and (ii) discharge cycles of the as-assembled half-cell based on recovered electrode material/Li foil after 100 cycles.
- Fig. 20 is a schematic diagram of sulphate-assisted separation of black mass from current collector by sonication.
- Fig. 21 is a schematic diagram of a conventional approach of recycling spent commercial batteries and/or capacitors versus the method of the present invention.
- Fig. 1(a) an overview of the recovery of electrode materials from spent batteries or capacitors using the method disclosed herein is illustrated.
- the presently disclosed method facilitates the direct recycling process through the separation of electrode materials from current collectors using the solutions of the present invention and allows for the direct use of recovered electrode materials in batteries or capacitors.
- spent batteries or capacitors are placed into a shredder where the batteries/capacitors are shredded (1) to expose internal components such as electrode materials and current collectors.
- the shredded batteries/capacitors are then immersed in the solutions of the present invention and sonicated (2) to facilitate delamination/ dislodgement of the electrode materials from the current collectors.
- the solutions of the present invention also participate in the separation of electrode materials from the current collectors via a physical separation. The separation may be assisted by the presence of ions in the solution with the possible formation of hydrogen bonds between the anions, water molecules and electrode material.
- the separated electrode materials suspended in the solution are then further centrifuged (3) to separate the electrode materials from the solution before drying (4) in an oven to obtain recovered electrode materials for further applications (battery fabrication).
- the solution may be recovered and reused and recycled (5) for recycling a second (or more) batches of batteries/capacitors.
- FIG. 2(a) A system for carrying out the method of the present invention is shown in Fig. 2(a).
- the shredded batteries/capacitors and the solutions of the present invention are contained in a primary (inner) container which is then further contained in a secondary (outer) container.
- the primary container comprises holes which serve as a sieve for finer particles to pass through to the secondary container.
- the two containers then act as a sieve system to separate particles of different sizes.
- the containers containing the shredded battery materials and solutions are sonicated to dislodge/ delaminate the electrode materials from the current collectors.
- the sonication process assists in the separation of the finer electrode materials from the current collectors, allowing the separated electrode materials to pass through the holes into the secondary container.
- the larger current collectors remaining are then collected directly from the primary container.
- the separation of the electrode materials and current collector is then accomplished by the simple and straightforward removal of the primary container from the secondary container.
- Fig. 2(b) further illustrates the separation
- current approaches to recycle spent batteries and/or capacitors such as hydrometallurgy and pyrometallurgy processes comprise shredding (A) to obtain shredded batteries and/or capacitors.
- An additional grinding step (B) is often required to further break up all the components in the shredded batteries and/or capacitors comprising current collectors and electrode materials, to form a powdered black mass.
- Hydrometallurgical processes such as leaching the black mass with strong acids (C) are often used to dissolve components which are then filtered.
- the treated materials then require further processing (D) such as re-calcination with metal precursors of recovered electrode materials before they can be reused in the synthesis (E) of new batteries/capacitors.
- the present invention may not require an additional grinding step and uses the solutions disclosed herein to separate electrode materials from current collectors directly. Furthermore, the present invention may not require post-processing and allows for the recovered electrode materials to be used directly in the synthesis of new batteries/capacitors.
- a major disadvantage of such grinding step may include the intermixing of current collector materials with the electrode materials in the powdered black mass, which may be easily avoided and circumvented with the present invention. Leaching of the black mass with strong acids may further dissolve current collectors such as aluminium and copper and increase the difficulty for further processing during extraction and separation. In addition, the exposure to harsh environments (e.g. strong acids) would lead to further complications in direct recycling of the active electrode materials.
- the inventors employed non-toxic and environmentally friendly rainwater and formulated green solutions to recycle spent commercial batteries and/or capacitors by delaminating/ dislodging electrode materials from current collectors, thereby obviating the need for strong acids and harsh conditions.
- the present invention may not require extensive post-treatment in the recovery of electrode materials for direct use in new batteries and/or capacitors.
- the present invention comprises a method of recovering electrode material from a battery or capacitor using non-toxic and environmentally friendly solutions.
- the method may enable the physical separation of electrode materials from current collectors and may allow for the recovered electrode materials to be used directly in further applications in batteries and capacitors.
- the present invention may not require an additional step of grinding the shredded batteries and/or capacitors into powdered form, allowing for the separation of current collectors from electrode materials in their original states without any chemical changes to material composition.
- the present invention may not require further post-processing (e.g., leaching or re-calcination with lithium precursors) of the recovered electrode materials and allows for the recovered electrode materials in the form of metal/ mixed metal oxides, metal/ mixed metal phosphates and/or metal/ mixed metal silicates to be directly used as the cathode/anode materials for battery applications.
- further post-processing e.g., leaching or re-calcination with lithium precursors
- the recovered electrode material obtained by the presently disclosed method may comprise one or more metal/mixed metal oxides, metal/mixed metal phosphates, or metal/mixed metal silicates as cathode materials, and carbonaceous material (such as carbon, hydrocarbons, graphite) or silicates/silicon-based materials (such as elemental silicon (Si), silicon oxides (SiO, SiO ) and silicon- based composites (e.g. SiCF/C)) as anode materials.
- carbonaceous material such as carbon, hydrocarbons, graphite
- silicates/silicon-based materials such as elemental silicon (Si), silicon oxides (SiO, SiO ) and silicon- based composites (e.g. SiCF/C)
- the present invention relates to a method of recovering electrode material from a battery or capacitor, wherein an electrode of the battery or capacitor is exposed to a solution comprising sulphate, phosphate, nitrate and/or chloride ions.
- the electrode may be an anode and/or a cathode.
- the electrode material may comprise metal oxides, metal phosphates, metal silicates, mixed metal oxides, mixed metal phosphates and/or mixed metal silicates, elemental silicon, silicon oxides, carbonaceous materials, carbon, hydrocarbons and/or polymers.
- the metal or mixed metal is selected from the group consisting of lithium, cobalt, nickel, aluminium, manganese, chromium, iron, titanium, and combinations thereof.
- the electrode material may be selected from the group consisting of lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium titanium oxide, lithium nickel oxide, lithium manganese dioxide, lithium manganese nickel oxide, lithium nickel cobalt aluminium oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium manganese phosphate, lithium nickel phosphate, lithium cobalt phosphate and lithium manganese silicate.
- the present invention may not require such highly acidic environments.
- the non-toxic and environmentally friendly rainwater and formulated green solutions disclosed herein have mild pH values which are very unlikely to pose health and environmental risks.
- the pH of the solution may be in the range of about 4 to about 7, from about 4 to about
- the mild pH values of the solutions disclosed herein may be an inherent result of dissolving metal salts and/or ammonium salts of anions with weak acid strengths.
- the solution may comprise metal salts and/or ammonium salts of sulphate, phosphate, nitrate and/or chloride, while the metal of the metal salt may be selected from the group consisting of lithium, sodium, magnesium, zinc, and aluminium.
- the solution may be selected from the group consisting of:
- the solution may comprise sulphate, phosphate, chloride, and nitrate anions in different concentrations with respect to one another.
- the solution may be selected from the group consisting of:
- solution A comprising chloride and nitrate ions, and solution B comprising sulphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B is in the range of about 2:8 to about 8:2;
- solution A comprising chloride and nitrate ions, and solution C comprising phosphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution C is in the range of about 2:8 to about 8:2;
- solution A comprising chloride and nitrate ions, solution B comprising sulphate, and solution C comprising phosphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B to solution C is in the range of about (2 to 4):(2 to 4):(2 to 4).
- the solution of the present invention may comprise sulphate and phosphate ions in a ratio of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
- the solution may comprise solution A and solution B, wherein solution A comprises chloride and nitrate ions, and wherein solution B comprises sulphate ions.
- the ratio of chloride to nitrate ions in solution A is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B is in the range of about 2:8 to about 8:2.
- the ratio of chloride to nitrate ions in solution A is in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
- the ratio of solution A to solution B is in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
- the solution of the present invention may comprise solution A and solution C, wherein solution A comprises chloride and nitrate ions, and wherein solution C comprises phosphate ions.
- solution A comprises chloride and nitrate ions
- solution C comprises phosphate ions.
- the ratio of chloride to nitrate ions in solution A is in the range of about 2:8 to about 8:2
- the ratio of solution A to solution C is in the range of about 2:8 to about 8:2.
- the ratio of chloride to nitrate ions in solution A may be in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
- the ratio of solution A to solution C may be in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
- the solution may comprise solution A, solution B and solution C, wherein solution A comprises chloride and nitrate ions, solution B comprises sulphate ions, and solution C comprises phosphate ions.
- the ratio of chloride to nitrate ions in solution A is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B to solution C is in the range of about (2 to 4): (2 to 4): (2 to 4).
- the ratio of chloride to nitrate ions in solution A may be in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
- the ratio of solution A to solution B to solution C may be in the range of about 2:2:2 (1:1:1), about 2:2:3, about 2:2:4, about 2:3:2, about 2:3:3, about 2:3:4, about 2:4:2, about 2:4:3, about 2:4:4, about 3:2:2, about 3:2:3, about 3:2:4, about 3:3:2, about 3:3:4, about 3:4:2, about 3:4:3, about 3:4:4, about 4:2:2, about 4:2:3, about 4:2:4, about 4:3:2, about 4:3:3, about 4:3:4, about 4:4:2, about 4:4:3, or any ranges or values therebetween.
- the concentration of sulphate, phosphate, nitrate and/or chloride ions in the solution may be about 0.3 M to about 2 M, about 0.3 M to about 1.5 M, about 0.3 M to about 1 M, about 0.3 M to about 0.75 M, about 0.3 M to about 0.6 M, about 0.3 M to about 0.5 M, about 0.3 M to about 0.4 M, about 0.4 M to about 2 M, about 0.4 M to about 1.5 M, about 0.4 M to about 1 M, about 0.4 M to about 0.75 M, about 0.4 M to about 0.6 M, about 0.4 M to about 0.5 M, about 0.5 M to about 2 M, about 0.5 M to about 1.5 M, about 0.5 M to about 1 M, about 0.5 M to about 0.75 M, about 0.5 M to about 0.6 M, about 0.6 M to about 2 M, about 0.6 M to about 1.5 M, about 0.6 M to about 1 M, about 0.5 M to about 0.75 M, about 0.5 M to about 0.6 M, about 0.6 M to about 2 M
- Additives may include surfactants which can reduce degradation of the structural integrity in the recovered materials during the separation process.
- the solution may further comprise a sulphate-containing surfactant.
- the surfactant may be selected from a group consisting of ammonium lauryl sulphate, sodium laureth sulphate, sodium myreth sulphate, sodium pareth sulphate, ammonium laureth sulphate, sodium lauryl sulphate, and sodium dodecyl sulphate (SDS).
- the concentration of sulphate ions in the surfactant may be about 0.01 M to about 0.85 M, about 0.01 M to about 0.8 M, about 0.01 M to about 0.75 M, about 0.01 M to about 0.7 M, about 0.01 M to about 0.65 M, about 0.01 M to about 0.6 M, about 0.01 M to about 0.55 M, about 0.01 M to about 0.5 M, about 0.01 M to about 0.45 M, about 0.01 M to about 0.4 M, about 0.01 M to about 0.35 M, about 0.01 M to about 0.3 M, about 0.01 M to about 0.25 M, about 0.01 M to about 0.2 M, about 0.01 M to about 0.15 M, about 0.01 M to about 0.1 M, about 0.01 M to about 0.05 M, about 0.05 M to about 0.85 M, about 0.05 M to about 0.8 M, about 0.05 M to about 0.75 M, about 0.05 M to about 0.7 M, about 0.05 M to about 0.65 M, about 0.05 M to about 0.6 M, about 0.05 M to about 0.55
- the method disclosed herein may further comprise recovering current collectors, which may comprise copper, aluminium, nickel, titanium, platinum, zinc, stainless steel, carbonaceous materials, and carbon.
- Carbonaceous materials may comprise carbon-fibres, carbon wires and carbon cloth.
- the method may further comprise agitating the solution.
- the agitation may comprise stirring, shaking, bubbling, recirculating or sonicating the solution.
- the method disclosed herein may not require heating or elevated temperatures and may be performed at room temperatures.
- the temperature of the solution before agitation/sonication may be in a range of at least about 10 °C, at least about 15 °C, at least about 20 °C, at least about 23 °C, at least about 25 °C, at least about 30 °C, at least about 40 °C, at least about 50 °C; or from about 10 °C to about 50 °C, from about 10 °C to about 40 °C, from about 10 °C to about 30 °C, from about 10 °C to about 25 °C, from about 10 °C to about 23 °C, from about 10 °C to about 20 °C, from about 10 °C to about 15 °C, from about 15 °C to about 50 °C, from about 15 °C to about 40 °C, from about 15 °C to about 30 °C, from about 15 °C to about 25 °C, from about 15 °C to about 23 °C, from about 15 °C to about 20 °C,
- the sonication is performed with the temperature of the solution at 23 °C.
- Agitation/sonication of solutions may cause a rise in temperature in liquids due to different processes such as adiabatic heating, molecular friction, energy dissipation within the liquid, and localized heating caused by cavitation.
- the rise in temperature of the solution after agitation/sonication is an expected phenomenon.
- the temperature of the solution after agitation/sonication is at a range of at least about 10 °C, at least about 15 °C, at least about 20 °C, at least about 23 °C, at least about 25 °C, at least about 30 °C, at least about 40 °C, at least about 50 °C; least about 60 °C, at least about 70 °C, at least about 80 °C, at least about 90 °C; or from about 10 °C to about 90 °C, from about 10 °C to about 80 °C, from about 10 °C to about 70 °C, from about 10 °C to about 60 °C, from about 10 °C to about 50 °C, from about 10 °C to about 40 °C, from about 10 °C to about 30 °C, from about 10 °C to about 25 °C, from about 10 °C to about 23 °C, from about 10 °C to about 20 °C, from about 10 °C to about 15
- the solution disclosed herein may not comprise metal ions leached from the batteries and/or capacitors.
- the solution may not contain dissolved metal ions from the batteries and/or capacitors and may remain in their original states without changes in their chemical compositions.
- the present invention discloses a physical separation of the recovered electrode material from the current collectors without dissolution of metals, metal oxides, metal phosphates, metal silicates, mixed metal oxides, mixed metal phosphates and/or mixed metal silicates from the batteries and/or capacitors into the solution.
- the separation may be assisted by the presence of sulphates with the possible formation of hydrogen bonds between the anions, water molecules and the black mass (Fig. 20).
- the separation may also be further assisted by the presence of bubbles (cavitation) in the solutions shown in Fig. 20.
- the present invention also discloses a battery or capacitor comprising the recovered electrode material disclosed herein.
- the present invention also discloses an electrode material obtained by the method disclosed herein.
- the recovered electrode material may be used in cathode and/or anode applications.
- the recovered electrode material may be regenerated as a cathode by reacting with lithium precursors.
- the recovered electrode material may be used as an anode by mixing the recovered electrode materials with carbon and binders on metal foils.
- the process of directly using recovered electrode material in new batteries/capacitors may allow for a sustainable approach towards battery /capacitor manufacturing, and the recovery and reintegration of the recovered electrode materials offer several advantages as follow below.
- the process helps reduce the environmental impact associated with battery production. By reusing electrode materials, the need for mining and extracting new resources is minimized, leading to a decrease in energy consumption and greenhouse gas emissions. Additionally, it helps mitigate the disposal of potentially hazardous materials from spent batteries, reducing the risk of soil and water contamination.
- the recovered electrode materials are deemed suitable for reuse, they can be integrated into the manufacturing of new batteries. These materials may be combined with newly sourced components to create hybrid electrode structures, optimizing the performance and longevity of the battery cells. The reintegration of recovered materials may occur in various battery chemistries, including lithium-ion, nickel-metal hydride, or even emerging technologies like solid- state batteries.
- the battery or capacitor comprising the recovered electrode material obtained from the method disclosed herein may have high galvanostatic charge and discharge capacities with stable electrochemical performance even after multiple cycles, showcasing that the present invention may offer great potential and advantages in reducing the environmental footprint and dependence on raw materials. This would allow for a more sustainable and circular approach within the battery /capacitor industry, supporting the transition towards a greener and more resource -efficient future.
- Example lb Sulphate -based Solutions with Surfactant
- Example ld(i) Mixed monovalent cationic salt solution (NaCl + L1NO3+ NaNO3) [Table 2, Solution 11
- Solution 4 Solution 2
- Solution s 0:1:1 4
- Solution 5 Solution 1 Solution 2 - 1:1:0 5 A mixture of complex salt solution and sulphates- based solution
- Solution 6 Solution 1 - Solution s 1:0:1 4 A mixture of complex salt solution and phosphates- based solution
- Solution 7 Solution 1 Solution 2 Solution s 1: 1:1 4 A mixture of complex salt solution, sulphates and
- the dominant Raman bands corresponding to the different components of the solution were labelled “X”, “Y” and “Z”.
- the Raman band region labelled X a corresponds to the different monovalent and multivalent cations -based sulphates components while the Raman band regions labelled Yi and Y2 correspond to the DI H2O component.
- Example 2a(i) Raman Spectra of Monovalent cationic (Li + /Na + /NH4 + ) sulphate solutions (Example la(i))
- Example 2b(i) Raman Spectrum of Mixed solution with SDS at 1:1 v/v (Example lb(ii))
- Example lb(ii) The mixed (NH4)SCC solution with SDS at 1:1 v/v of Example lb(ii) was identified through the distinct Raman bands of SDS appearing in the regions labelled “Zi” and “Z2” (Fig. 5a), together with the Raman bands in regions “X a ”, “Yi” and “Y2”.
- Example la(vi) The mixed A ⁇ SCbb solution with SDS at 1:1 v/v of Example la(vi) was identified through the distinct Raman bands of SDS appearing in the regions labelled “Zi” and “Z2” (Fig. 5b), together with the Raman bands in regions “X a ”, “Yi” and “Y2”.
- the characteristic Raman bands of the SDS surfactant were identified through the distinct peaks appearing in the regions labelled “Zi” and “Z2” in the Raman spectrum (Figs. 5a-5b).
- Example 2d(i) Raman Spectrum of mixed monovalent cationic salt solution (NaCl + LiN03+ NaNO3) (Example ld(i))
- a control solution with sulphate-based solution with Example ld(ii) was identified through the Raman bands which consists of Raman bands of the control solution as well as the other Raman bands corresponding to the sulphate-based solution (Fig. 7(b)).
- a control solution with phosphate-based solution with Example Id(iii) was identified through the Raman bands which consist of Raman bands of the control solution as well as the other Raman bands corresponding to the phosphate-based solution (Fig. 7(c)).
- a control solution with sulphate-based and phosphate-based solution with Example ld(iv) was identified through the Raman bands which consist of Raman bands of the control solution as well as the other Raman bands corresponding to the sulphate- and phosphate-based solutions (Fig. 7(d)).
- Example 1 Using DI water and rainwater as control solutions, the formulated 0.5M sulphate-based solutions comprising Li, Na, NH4, Mg, Zn and Al cations in Example 1 were measured using pH- indicator strips and were found to be between pH 4 to 7 (Fig. 3). Di-water and rainwater were found to have a pH value of ⁇ 4. Li- and Zn- based sulphates solutions were found to have a pH value of ⁇ 5. Na-, NH4-, Mg- based sulphates solutions were found to have a pH value of ⁇ 6. Al- based sulphate solution was found to have a pH value of ⁇ 4.
- Spent batteries were placed into a shredder where the batteries/capacitors were physically shredded and the internal components such as electrode materials and current collectors were exposed (Fig. 1(b)).
- the shredded batteries/capacitors are then immersed in the solutions of Example 1 and sonicated to facilitate dislodgement/delamination of the electrode materials from the current collectors.
- a sieve system may be employed to facilitate the separation (Fig. 2).
- the sieve system consists of two containers, with a primary (inner) container having two rows of designated placement of 3 mm holes that functions as a sieve while the outer container functions as a secondary containment container (Fig. 2(a)).
- the containers containing the shredded battery/capacitor materials and solutions were then sonicated to dislodge/delaminate the electrode materials from the current collectors.
- the sonication process assists in the separation of the separated finer electrode materials from the larger current collectors, allowing the separated electrode materials to pass through the holes into the secondary .
- the current collectors were then collected directly from in the primary (inner) container. The separation of the recovered electrode materials and the current collectors was achieved by the simple and straightforward removal of the primary container from the secondary container.
- Example 3b Recycling of Solution
- Example 3c The solutions recovered in Example 3c may then be reused for a next batch of recovery as described in Examples 3b and 3c.
- Rainwater was presented as an effective solution as compared to DI H2O (Fig. 10) to dislodge/ delaminate the electrode materials from the current collectors, despite both having similar solution structure based on confocal Raman spectroscopy results (Fig. 8). It was suggested that the presence of ions in the rainwater might be the key contribution factor for an ideal recycling solution. As the rainwater were known to contain nitric, sulphuric and hydrochloric acids, diluted H2SO4 and HNO3 (Fig. 10) were prepared as control samples for comparison purposes.
- the electrode sonicated in the DI H2O had the electrode materials remained largely intact and unseparated on the current collector (Fig. 11), in stark contrast, the electrode materials sonicated in sulphates-containing solution (e.g., rainwater or monovalent/multivalent cations - based, had the majority of their electrode materials dislodged/ delaminated from the aluminium current collector after 2 and 5 minutes of sonication at 25 °C respectively in Fig. 11.
- sulphates-containing solution e.g., rainwater or monovalent/multivalent cations - based
- the composite salt-based solutions based on NHA and Al 3+ sulphates with SDS were formulated according to Table 1 (Solution II and III respectively) and in Example lb(ii)-(iii).
- the single salt solution based on SDS in DI H2O was prepared as a control solution (Solution I) and according to Example lb(i).
- the electrode materials were completely removed without the breakage and corrosion of the aluminium current collector after the electrodes were sonicated in solution with SDS.
- the electrode sonicated in the control solution (Solution I) had the bulk of electrode materials intact on the aluminium collector, demonstrating the importance of composite salt-based solution for effective removal of the electrode materials from the current collector without any damage to the current collector.
- Example 4e Mixed Sulphate and/or Phosphate -based Solutions
- a series of solutions (Solution 1 to 7) was prepared according to Table 2 to evaluate the effect of mixed sulphates and/or phosphates -based solution in a complex solution environment (e.g., in a mixed cations and anions environment) for the delamination of electrodes.
- the electrodes were placed into the respective solutions 1 to 7 in Fig. 14.
- Solution 1 was set as the control solution with no sulphates and phosphates anions present.
- the electrodes were then sonicated in the prepared solutions, with the results taken after a duration of 1 minute and 15 minutes respectively.
- the elemental composition and crystal structure of the recovered electrode materials were characterized using a scanning electron microscope (SEM) coupled with electron dispersive X-ray spectrometer (EDS) (JEOL FESEM 7600F) and X-ray diffractometer (Bruker D8 Advance), respectively. Match! software was used to analyze the X-ray diffraction pattern based on inorganic crystal structure database (ICSD). Based on the SEM -EDS measurement, the elemental compositions of Ni, Co, Al, O, and C were detected (Fig. 15). From the X-ray diffraction pattern of the recycled materials, a composite of lithium cobalt nickel aluminium oxides and carbon-based materials (carbon and graphite) were identified (Fig. 16).
- a slurry was prepared by mixing the recycled materials with conductive carbon black and polyvinylidene fluoride (PVDF) binder in a weight ratio of 8: 1 : 1. The slurry was then cast onto a copper foil using a doctor blade, followed by the overnight vacuum drying process. A half-cell configuration (Fig. 17) was assembled to test the electrode (active mass ⁇ 2 mg) as the anode (working electrode) with 16 mm lithium foil as counter and reference electrode.
- PVDF polyvinylidene fluoride
- a monolayer polypropylene (Celgard 2400) was employed as a separator while the 1 M LiPFe in ethylene carbonate (EC): ethyl methyl carbonate (EMC) 3:7 v/v was used as the electrolyte.
- the coin cell was then assembled in a glovebox under an inert argon environment.
- the half-cell was electrochemically cycled between the range of 0.005 V to 2.5 V at a current density of 300 mA g ⁇ with a rest time of 1 minute in between steps.
- the galvanostatic charge and discharge curves of the recovered materials/Li cell are shown in Fig. 18.
- the direct application of recovered electrode materials as the anode delivered a high discharge capacity of 446.4 mAh g 1 in the initial cycle at a current density of 300 mA g -1 .
- the cell also exhibited a stable electrochemical performance with a discharge capacity of -138.1 mAh g 1 after 100 cycles (Fig. 19).
- the present invention relates to a method of recovering electrode material from a battery or a capacitor, wherein an electrode of the battery or capacitor is exposed to a solution comprising sulphate, phosphate, nitrate and/or chloride ions.
- the solution in the method disclosed herein is environmentally friendly and non-hazardous, which obviates the need for conventional strong acids used in leaching or high energy input for pyrometallurgical means, and may not require extensive post-treatment steps to recover electrode materials .
- the disclosed method of recovering electrode material from a battery or a capacitor may be cost-effective, simple, environmentally friendly, and scalable in the manufacturing process for mass production.
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Abstract
The present disclosure provides for a method of recovering electrode material from a battery or capacitor, wherein an electrode of the battery or capacitor is exposed to a solution comprising sulphate, phosphate, nitrate and/or chloride ions. The present disclosure further provides for electrode material obtained by said method and a battery/capacitator comprising said electrode material.
Description
Method of Recovering Electrode Material
Technical Field
The present disclosure refers to a method of recovering electrode material from a battery or capacitor. The present disclosure also relates to electrode material obtained by the method, and a battery or capacitor comprising the electrode material.
Background Art
With the increasing battery production for applications in energy storage and powering of portable devices (e.g., phones, laptops, etc.) to electric vehicles, concerns have been raised over its impact on the sustainability of Earth’s resources and the environmental issues related to battery waste generated at the end of the lifecycle of batteries.
In this regard, several recycling technologies have been proposed. However, most of the processes commonly involve grinding the electrode materials together with current collectors into fine powders or using strong acids for the leaching of metal components. However, these methods encounter significant disadvantages. For example, grinding electrode materials together with current collectors is not an efficient way of recovering electrode material and complicates the process of separating current collectors from electrode material. Additionally, hydrometallurgical methods such as using strong acids for leaching are not environmentally friendly, are difficult to handle and may be hazardous to health.
Other methods of recycling include pyrometallurgical methods. However, such methods disadvantageously require high energy input due to the high temperatures required and may produce toxic gases which in turn require further treatment before releasing into the atmosphere.
There is therefore a need to provide a method of recovering electrode material from batteries or capacitors that overcomes, or at least ameliorates, one or more of the disadvantages described above.
Summary
In one aspect of the present disclosure, there is provided a method of recovering electrode material from a battery or capacitor, wherein an electrode of the battery or capacitor is exposed to a solution comprising sulphate, phosphate, nitrate and/or chloride ions.
Advantageously, the solution in the disclosed method may be non-hazardous and environmentally friendly. The solution recovers electrode material from spent batteries and/or capacitors by delaminating/dislodging electrode material from the current collectors without the use of
conventional strong acids to leach metal components, and also removes the need for high energy heating processes, such as melting the batteries and/or capacitors.
The presently disclosed method may also advantageously be performed under ambient conditions which avoid harsh conditions such as highly acidic environments which can result in leaching of metal components and high temperatures to melt the battery or capacitator (smelting), which may require high levels of energy input.
Advantageously, the presently disclosed method may not require grinding the electrode materials together with the current collectors into fine powders, which reduces the risks of releasing harmful pollutants, dust or fumes into the environment. Without the need for grinding, the disclosed method may also make it easier to separate and extract electrode materials and current collectors.
Unlike pyrometallurgical methods, the presently disclosed method may also advantageously not release or emit toxic gases or fumes which can pose both health and environmental risks, thereby removing the need for pre-treatment processes before the releasing into the environment.
Further advantageously, the solution may be cost-effective, non-toxic and environmentally friendly, allowing for a safe, sustainable, and scalable solution for large-scale direct recycling of batteries or capacitors.
Also advantageously, the presently disclosed method may comprise a facile and one-step separation of current collectors from electrode material, removing the need for further extraction or post-processing (e.g., leaching or re-calcination with metal precursors) of recovered electrode materials.
In another aspect of the present disclosure, there is provided a battery or capacitor comprising the recovered electrode material disclosed herein.
In a further aspect of the present disclosure, there is provided electrode material obtained by the method disclosed herein.
Advantageously, the presently disclosed method allows for the recovered electrode material to be directly used as electrode materials for battery/capacitor applications.
Further advantageously, the direct use of the recovered electrode materials may reduce energy consumption as compared to conventional hydrometallurgical and pyrometallurgical methods and may therefore reduce the overall cost of producing new batteries and/or capacitors. Recovering and reusing electrode materials may lower the expenses associated with sourcing and processing new raw materials, rendering lower costs and higher affordability for consumers.
More advantageously, direct recycling and reuse ensures hazardous materials such as heavy metals and toxic chemicals from batteries and capacitors may prevent environmental contamination by reducing the risk of these substances entering ecosystems, groundwater, or air when improperly disposed of. In addition, direct recycling and reuse of the recovered electrode
materials may help create a closed-loop system by reintroducing materials from used batteries or capacitors back into the production cycle. This promotes a circular economy approach, reducing waste and ensuring a sustainable supply of materials for future battery and capacitor production.
Definitions
Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings that are commonly understood by those of ordinary skill in the art. Generally, nomenclature used in connection with, and techniques of, chemistry described herein, are those well-known and commonly used in the art.
As used herein, the term "electrode material" refers to a material comprising either anode material, cathode material, or a mixture thereof. For example, the electrode material may comprise one or more of metal/mixed metal oxides (cathode material), metal/mixed metal phosphates (cathode material), or metal/mixed metal silicates (cathode material), carbonaceous material (such as carbon, hydrocarbons, graphite) (anode material), or silicon-based materials (anode material).
As used herein, the term “delamination” refers to the mechanical separation or detachment of electrode material from the surface of a current collector within an electrochemical system, typically in the context of energy storage devices such as batteries or capacitors. It encompasses the detachment of electrode active materials, binders, and conductive additives from the current collector's substrate. As used herein, the terms “delamination” and “dislodgement” are used interchangeably .
As used herein, the term “mixed metal” or “mixed metal material” includes any compound comprising at least two metals. By way of example, where the mixed metal material is obtained during the recycling of batteries/capacitors, the mixed metal material may comprise one or more metals that are present in said batteries/capacitors, such as those present in the electrodes (e.g. cathode and anode materials).
As used herein, the term “current collector” refers to a substrate for an electrode material able to conduct electrons. By way of example, current collector may comprise metal, metallic or conductive current collectors.
As used herein, the term “black mass” refers to a composition comprising electrode materials including electrode active materials, polymeric binder, residual current collector material, and other residual particulates. The chemical composition of black mass depends upon the chemistry of the battery/capacitor.
Unless the context requires otherwise or specifically stated to the contrary, integers, steps, or elements of the invention recited herein as singular integers, steps or elements clearly encompass both singular and plural forms of the recited integers, steps or elements.
Unless specified otherwise, the terms "comprising" and "comprise", and grammatical variants thereof, are intended to represent "open" or "inclusive" language such that they include recited elements but also permit inclusion of additional, unrecited elements.
As used herein, the term "about", in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
Throughout this disclosure, certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
Certain embodiments may also be described broadly and generically herein. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the disclosure. This includes the generic description of the embodiments with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.
Brief Description of Drawings
The accompanying drawings illustrate disclosed embodiments and serve to explain the principles of the disclosed embodiments. It is to be understood, however, that the drawings are designed for purposes of illustration only, and not as a definition of the limits of the invention.
Fig. l
Fig. 1 is a schematic diagram of a method of recycling of batteries and/or capacitors using the method
disclosed in the present invention to obtain current collector and electrode material. The obtained electrode material can be reused in new batteries and/or capacitors.
Fig. 2
Fig. 2 is a schematic diagram showing the use of an integrated sieve system in a method of the present invention.
Fig. 3
Fig. 3 is an image showing the pH values of various sulphate solutions.
Fig. 4
Fig. 4 is a series of Raman spectra of sulphate-based solutions of the present invention.
Fig. 5a
Fig. 5a is a series of Raman spectrums of NH4-based sulphates with SDS and without SDS.
Fig. 5b
Fig. 5b is a series of Raman spectra of Al-based sulphates with SDS and without SDS.
Fig. 6
Fig. 6 is a Raman spectrum showing the Raman bands of sulphates (Xa) and phosphates (Xb) of solutions of the present invention.
Fig. 7
Fig. 7 is a series of Raman spectra of solutions in Table 2: (a) control solution without sulphates and phosphates (Solution 1); (b) control with sulphates-based solution (Solution 2); (c) control with phosphates-based solution (Solution 3); and (d) control with sulphates- and phosphates-based solution (Solution 7).
Fig. 8
Fig. 8 is a series of graphs of confocal Raman spectrum of rainwater and DI water.
Fig. 9
Fig. 9 is a bar chart showing the concentration of Cl , NO3 and SO42 anions in rainwater in parts per million (ppm).
Fig. 10
Fig. 10 are photographs of electrodes after sonication using diluted H2SO4, diluted HNO3, deionized (DI) water, and rainwater (RW).
Fig. 11
Fig. 11 is a series of images of electrodes after sonication at 25 °C for 2 and 5 minutes using DI H2O, rainwater (RW), Li+-based solution, Na+-based solution, NHA-based solution, Mg2+-based solution, Zn2+-based solution, and Al3+-based solution.
Fig. 12
Fig. 12 is an image of two electrodes after sonication using phosphates-based and sulphates-based solutions.
Fig. 13
Fig. 13 is a series of images of electrodes after sonication for 1 minute, 4 minutes, 5 minutes and 10 minutes using different solutions comprising 0.5M sodium dodecyl sulphates (SDS). Images on the right are enlarged images of the electrodes at the respective time intervals and solutions.
Fig. 14
Fig. 14 is a series of images of electrodes in the respective solutions (1-7) after sonication at 25°C for 0 minutes, 1 minute, and 15 minutes.
Fig. 15
Fig. 15 is a series of scanning electron microscope (SEM) images of recovered electrode material.
Fig. 16
Fig. 16 is an X-ray diffraction (XRD) pattern of recovered electrode materials.
Fig. 17
Fig. 17 is a schematic diagram of an electrochemical cell configuration using recovered electrode materials as anodes.
Fig. 18
Fig. 18 is a graph showing the galvanostatic charge and discharge curves of recovered electrode materials/lithium (Li) foil at 300 mA g 1 after (i) 1; (ii) 2; (iii) 10; and (iv) 100 cycles.
Fig. 19
Fig. 19 is a graph showing the (i) charge and (ii) discharge cycles of the as-assembled half-cell based on recovered electrode material/Li foil after 100 cycles.
Fig. 20
Fig. 20 is a schematic diagram of sulphate-assisted separation of black mass from current collector by sonication.
Fig. 21
Fig. 21 is a schematic diagram of a conventional approach of recycling spent commercial batteries and/or capacitors versus the method of the present invention.
Detailed Disclosure of Drawings
Referring to Fig. 1(a), an overview of the recovery of electrode materials from spent batteries or capacitors using the method disclosed herein is illustrated. The presently disclosed method facilitates the direct recycling process through the separation of electrode materials from current collectors using the solutions of the present invention and allows for the direct use of recovered electrode materials in batteries or capacitors.
Referring to Fig. 1(b), spent batteries or capacitors are placed into a shredder where the batteries/capacitors are shredded (1) to expose internal components such as electrode materials and current collectors. The shredded batteries/capacitors are then immersed in the solutions of the present invention and sonicated (2) to facilitate delamination/ dislodgement of the electrode materials from the current collectors. The solutions of the present invention also participate in the separation of electrode materials from the current collectors via a physical separation. The separation may be assisted by the presence of ions in the solution with the possible formation of hydrogen bonds between the anions, water molecules and electrode material. The separated electrode materials suspended in the solution are then further centrifuged (3) to separate the electrode materials from the solution before drying (4) in an oven to obtain recovered electrode materials for further applications (battery fabrication). The solution may be recovered and reused and recycled (5) for recycling a second (or more) batches of batteries/capacitors.
A system for carrying out the method of the present invention is shown in Fig. 2(a). The shredded batteries/capacitors and the solutions of the present invention are contained in a primary (inner) container which is then further contained in a secondary (outer) container. The primary container comprises holes which serve as a sieve for finer particles to pass through to the secondary container. The two containers then act as a sieve system to separate particles of different sizes. The containers containing the shredded battery materials and solutions are sonicated to dislodge/ delaminate the electrode materials from the current collectors. The sonication process assists in the separation of the
finer electrode materials from the current collectors, allowing the separated electrode materials to pass through the holes into the secondary container. The larger current collectors remaining are then collected directly from the primary container. The separation of the electrode materials and current collector is then accomplished by the simple and straightforward removal of the primary container from the secondary container. Fig. 2(b) further illustrates the separation process of Fig. 2(a).
Referring to Fig. 21, current approaches to recycle spent batteries and/or capacitors such as hydrometallurgy and pyrometallurgy processes comprise shredding (A) to obtain shredded batteries and/or capacitors. An additional grinding step (B) is often required to further break up all the components in the shredded batteries and/or capacitors comprising current collectors and electrode materials, to form a powdered black mass. Hydrometallurgical processes such as leaching the black mass with strong acids (C) are often used to dissolve components which are then filtered. The treated materials then require further processing (D) such as re-calcination with metal precursors of recovered electrode materials before they can be reused in the synthesis (E) of new batteries/capacitors. Unlike current approaches, the present invention may not require an additional grinding step and uses the solutions disclosed herein to separate electrode materials from current collectors directly. Furthermore, the present invention may not require post-processing and allows for the recovered electrode materials to be used directly in the synthesis of new batteries/capacitors.
Detailed Disclosure of Embodiments
The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application and uses of the invention. Furthermore, there is no intention to be bound by any theory presented in the preceding background of the invention or the following detailed description.
Current approaches to recycle spent batteries and/or capacitors, which include but are not limited to hydrometallurgy and pyrometallurgy, may very often require an additional grinding step to break up all the components such as current collectors and electrode materials in the shredded batteries and/or capacitors into a powdered form. A major disadvantage of such grinding step may include the intermixing of current collector materials with the electrode materials in the powdered black mass, which may be easily avoided and circumvented with the present invention. Leaching of the black mass with strong acids may further dissolve current collectors such as aluminium and copper and increase the difficulty for further processing during extraction and separation. In addition, the exposure to harsh environments (e.g. strong acids) would lead to further complications in direct recycling of the active electrode materials.
To address the challenges discussed, the inventors employed non-toxic and environmentally friendly rainwater and formulated green solutions to recycle spent commercial
batteries and/or capacitors by delaminating/ dislodging electrode materials from current collectors, thereby obviating the need for strong acids and harsh conditions. Unlike conventional methods, the present invention may not require extensive post-treatment in the recovery of electrode materials for direct use in new batteries and/or capacitors.
The present invention comprises a method of recovering electrode material from a battery or capacitor using non-toxic and environmentally friendly solutions. The method may enable the physical separation of electrode materials from current collectors and may allow for the recovered electrode materials to be used directly in further applications in batteries and capacitors.
In particular, the present invention may not require an additional step of grinding the shredded batteries and/or capacitors into powdered form, allowing for the separation of current collectors from electrode materials in their original states without any chemical changes to material composition.
Furthermore, the present invention may not require further post-processing (e.g., leaching or re-calcination with lithium precursors) of the recovered electrode materials and allows for the recovered electrode materials in the form of metal/ mixed metal oxides, metal/ mixed metal phosphates and/or metal/ mixed metal silicates to be directly used as the cathode/anode materials for battery applications.
The recovered electrode material obtained by the presently disclosed method may comprise one or more metal/mixed metal oxides, metal/mixed metal phosphates, or metal/mixed metal silicates as cathode materials, and carbonaceous material (such as carbon, hydrocarbons, graphite) or silicates/silicon-based materials (such as elemental silicon (Si), silicon oxides (SiO, SiO ) and silicon- based composites (e.g. SiCF/C)) as anode materials.
The present invention relates to a method of recovering electrode material from a battery or capacitor, wherein an electrode of the battery or capacitor is exposed to a solution comprising sulphate, phosphate, nitrate and/or chloride ions.
The electrode may be an anode and/or a cathode.
The electrode material may comprise metal oxides, metal phosphates, metal silicates, mixed metal oxides, mixed metal phosphates and/or mixed metal silicates, elemental silicon, silicon oxides, carbonaceous materials, carbon, hydrocarbons and/or polymers. The metal or mixed metal is selected from the group consisting of lithium, cobalt, nickel, aluminium, manganese, chromium, iron, titanium, and combinations thereof.
The electrode material may be selected from the group consisting of lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium titanium oxide, lithium nickel oxide, lithium manganese dioxide, lithium manganese nickel oxide, lithium nickel cobalt aluminium oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium manganese phosphate, lithium nickel phosphate, lithium cobalt phosphate and lithium manganese silicate.
Unlike conventional approaches where strong acids are used for leaching of metals, the present invention may not require such highly acidic environments. The non-toxic and environmentally friendly rainwater and formulated green solutions disclosed herein have mild pH values which are very unlikely to pose health and environmental risks.
The pH of the solution may be in the range of about 4 to about 7, from about 4 to about
6.5, from about 4 to about 6, from about 4 to about 5.5, from about 4 to about 5, from about 4 to about 4.5, from about 4.5 to about 7, from about 4.5 to about 6.5, from about 4.5 to about 6, from about 4.5 to about 5.5, from about 4.5 to about 5, from about 5 to about 7, from about 5 to about
6.5, from about 5 to about 6, from about 5 to about 5.5, from about 5.5 to about 7, from about 5.5 to about 6.5, from about 5.5 to about 6, from about 6 to about 7, from about 6 to about 6.5, from about 6.5 to about 7, or at most about 4, or at most about 4.5, or at most about 5, or at most about
5.5, at most about 6, at most about 6.5, at most about 7; or about 4, about 4.5, about 5, about 5.5, about 6, about 6.5, about 7, or any ranges or values therebetween.
The mild pH values of the solutions disclosed herein may be an inherent result of dissolving metal salts and/or ammonium salts of anions with weak acid strengths.
The solution may comprise metal salts and/or ammonium salts of sulphate, phosphate, nitrate and/or chloride, while the metal of the metal salt may be selected from the group consisting of lithium, sodium, magnesium, zinc, and aluminium.
The solution may be selected from the group consisting of:
(i) solution comprising sulphate ions;
(ii) solution comprising phosphate ions;
(iii) solution comprising sulphate and phosphate ions;
(iv) solution comprising chloride, nitrate and sulphate ions;
(v) solution comprising chloride, nitrate, and phosphate ions; and
(vi) solution comprising chloride, nitrate, sulphate, and phosphate ions.
In addition, the solution may comprise sulphate, phosphate, chloride, and nitrate anions in different concentrations with respect to one another.
Specifically, the solution may be selected from the group consisting of:
(i) solution comprising sulphate ions;
(ii) solution comprising phosphate ions;
(iii) solution comprising sulphate and phosphate ions in a ratio of about 2:8 to about 8:2;
(iv) solution A comprising chloride and nitrate ions, and solution B comprising sulphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B is in the range of about 2:8 to about 8:2;
(v) solution A comprising chloride and nitrate ions, and solution C comprising phosphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution C is in the range of about 2:8 to about 8:2; and
(vi) solution A comprising chloride and nitrate ions, solution B comprising sulphate, and solution C comprising phosphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B to solution C is in the range of about (2 to 4):(2 to 4):(2 to 4).
The solution of the present invention may comprise sulphate and phosphate ions in a ratio of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
The solution may comprise solution A and solution B, wherein solution A comprises chloride and nitrate ions, and wherein solution B comprises sulphate ions. In such embodiments, the ratio of chloride to nitrate ions in solution A is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B is in the range of about 2:8 to about 8:2.
In some embodiments, the ratio of chloride to nitrate ions in solution A is in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
In some embodiments, the ratio of solution A to solution B is in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about
4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
The solution of the present invention may comprise solution A and solution C, wherein solution A comprises chloride and nitrate ions, and wherein solution C comprises phosphate ions. In such embodiments, the ratio of chloride to nitrate ions in solution A is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution C is in the range of about 2:8 to about 8:2.
The ratio of chloride to nitrate ions in solution A may be in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
The ratio of solution A to solution C may be in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about 6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
The solution may comprise solution A, solution B and solution C, wherein solution A comprises chloride and nitrate ions, solution B comprises sulphate ions, and solution C comprises phosphate ions. In such embodiments, the ratio of chloride to nitrate ions in solution A is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B to solution C is in the range of about (2 to 4): (2 to 4): (2 to 4).
The ratio of chloride to nitrate ions in solution A may be in the range of about 2:8 to about 8:2, about 2:8 to about 7:3, about 2:8 to about 6:4, about 2:8 to about 5:5, about 2:8 to about 4:6, about 2:8 to about 3:7, about 3:7 to about 8:2, about 3:7 to about 7:3, about 3:7 to about 6:4, about 3:7 to about 5:5, about 3:7 to about 4:6, about 4:6 to about 8:2, about 4:6 to about 7:3, about 4:6 to about 6:4, about 4:6 to about 5:5, about 5:5 to about 8:2, about 5:5 to about 7:3, about 5:5 to about
6:4, about 6:4 to about 8:2, about 6:4 to about 7:3, about 7:3 to about 8:2, or any ranges or values therebetween.
The ratio of solution A to solution B to solution C may be in the range of about 2:2:2 (1:1:1), about 2:2:3, about 2:2:4, about 2:3:2, about 2:3:3, about 2:3:4, about 2:4:2, about 2:4:3, about 2:4:4, about 3:2:2, about 3:2:3, about 3:2:4, about 3:3:2, about 3:3:4, about 3:4:2, about 3:4:3, about 3:4:4, about 4:2:2, about 4:2:3, about 4:2:4, about 4:3:2, about 4:3:3, about 4:3:4, about 4:4:2, about 4:4:3, or any ranges or values therebetween.
More specifically, the concentration of sulphate, phosphate, nitrate and/or chloride ions in the solution may be about 0.3 M to about 2 M, about 0.3 M to about 1.5 M, about 0.3 M to about 1 M, about 0.3 M to about 0.75 M, about 0.3 M to about 0.6 M, about 0.3 M to about 0.5 M, about 0.3 M to about 0.4 M, about 0.4 M to about 2 M, about 0.4 M to about 1.5 M, about 0.4 M to about 1 M, about 0.4 M to about 0.75 M, about 0.4 M to about 0.6 M, about 0.4 M to about 0.5 M, about 0.5 M to about 2 M, about 0.5 M to about 1.5 M, about 0.5 M to about 1 M, about 0.5 M to about 0.75 M, about 0.5 M to about 0.6 M, about 0.6 M to about 2 M, about 0.6 M to about 1.5 M, about 0.6 M to about 1 M, about 0.6 M to about 0.75 M, about 0.75 M to about 2 M, about 0.75 M to about 1.5 M, about 0.75 M to about 1 M, about 1 M to about 2 M, about 1 M to about 1.5 M, about 1.5 M to about 2 M, about 1 M to about 1.5 M, or any ranges or values therebetween.
Besides the extraction of the electrode materials, it is of great importance that other materials, such as current collectors, are to be recovered are in their original states without degradation, loss of mass or change in chemical composition in the method disclosed herein. In the presence of certain additives, the quality of the other recovered materials may be enhanced when used with the method disclosed herein. Additives may include surfactants which can reduce degradation of the structural integrity in the recovered materials during the separation process.
Specifically, the solution may further comprise a sulphate-containing surfactant.
The surfactant may be selected from a group consisting of ammonium lauryl sulphate, sodium laureth sulphate, sodium myreth sulphate, sodium pareth sulphate, ammonium laureth sulphate, sodium lauryl sulphate, and sodium dodecyl sulphate (SDS).
The concentration of sulphate ions in the surfactant may be about 0.01 M to about 0.85 M, about 0.01 M to about 0.8 M, about 0.01 M to about 0.75 M, about 0.01 M to about 0.7 M, about 0.01 M to about 0.65 M, about 0.01 M to about 0.6 M, about 0.01 M to about 0.55 M, about 0.01 M to about 0.5 M, about 0.01 M to about 0.45 M, about 0.01 M to about 0.4 M, about 0.01 M to about 0.35 M, about 0.01 M to about 0.3 M, about 0.01 M to about 0.25 M, about 0.01 M to about
0.2 M, about 0.01 M to about 0.15 M, about 0.01 M to about 0.1 M, about 0.01 M to about 0.05 M, about 0.05 M to about 0.85 M, about 0.05 M to about 0.8 M, about 0.05 M to about 0.75 M, about 0.05 M to about 0.7 M, about 0.05 M to about 0.65 M, about 0.05 M to about 0.6 M, about 0.05 M to about 0.55 M, about 0.05 M to about 0.5 M, about 0.05 M to about 0.45 M, about 0.05 M to about 0.4 M, about 0.05 M to about 0.35 M, about 0.05 M to about 0.3 M, about 0.05 M to about 0.25 M, about 0.05 M to about 0.2 M, about 0.05 M to about 0.15 M, about 0.05 M to about 0.1 M, about 0.1 M to about 0.85 M, about 0.1 M to about 0.8 M, about 0.1 M to about 0.75 M, about 0.1 M to about 0.7 M, about 0.1 M to about 0.65 M, about 0.1 M to about 0.6 M, about 0.1 M to about 0.55 M, about 0.1 M to about 0.5 M, about 0.1 M to about 0.45 M, about 0.1 M to about 0.4 M, about 0.1 M to about 0.35 M, about 0.1 M to about 0.3 M, about 0.1 M to about 0.25 M, about 0.1 M to about 0.2 M, about 0.1 M to about 0.15 M, about 0.15 M to about 0.85 M, about 0.15 M to about 0.8 M, about 0.15 M to about 0.75 M, about 0.15 M to about 0.7 M, about 0.15 M to about 0.65 M, about 0.15 M to about 0.6 M, about 0.15 M to about 0.55 M, about 0.15 M to about 0.5 M, about 0.15 M to about 0.45 M, about 0.15 M to about 0.4 M, about 0.15 M to about 0.35 M, about 0.15 M to about 0.3 M, about 0.15 M to about 0.25 M, about 0.15 M to about 0.2 M, about 0.2 M to about 0.85 M, about 0.2 M to about 0.8 M, about 0.2 M to about 0.75 M, about 0.2 M to about 0.7 M, about 0.2 M to about 0.65 M, about 0.2 M to about 0.6 M, about 0.2 M to about 0.55 M, about 0.2 M to about 0.5 M, about 0.2 M to about 0.45 M, about 0.2 M to about 0.4 M, about 0.2 M to about 0.35 M, about 0.2 M to about 0.3 M, about 0.2 M to about 0.25 M, about 0.25 M to about 0.85 M, about 0.25 M to about 0.8 M, about 0.25 M to about 0.75 M, about 0.25 M to about 0.7 M, about 0.25 M to about 0.65 M, about 0.25 M to about 0.6 M, about 0.25 M to about 0.55 M, about 0.25 M to about 0.5 M, about 0.25 M to about 0.45 M, about 0.25 M to about 0.4 M, about 0.25 M to about 0.35 M, about 0.25 M to about 0.3 M, about 0.3 M to about 0.85 M, about 0.3 M to about 0.8 M, about 0.3 M to about 0.75 M, about 0.3 M to about 0.7 M, about 0.3 M to about 0.65 M, about 0.3 M to about 0.6 M, about 0.3 M to about 0.55 M, about 0.3 M to about 0.5 M, about 0.3 M to about 0.45 M, about 0.3 M to about 0.4 M, about 0.3 M to about 0.35 M, about 0.35 M to about 0.85 M, about 0.35 M to about 0.8 M, about 0.35 M to about 0.75 M, about 0.35 M to about 0.7 M, about 0.35 M to about 0.65 M, about 0.35 M to about 0.6 M, about 0.35 M to about 0.55 M, about 0.35 M to about 0.5 M, about 0.35 M to about 0.45 M, about 0.35 M to about 0.4 M, about 0.4 M to about 0.85 M, about 0.4 M to about 0.8 M, about 0.4 M to about 0.75 M, about 0.4 M to about 0.7 M, about 0.4 M to about 0.65 M, about 0.4 M to about 0.6 M, about 0.4 M to about 0.55 M, about 0.4 M to about 0.5 M, about 0.4 M to about 0.45 M, about 0.45 M to about 0.85 M, about 0.45 M to about 0.8 M, about 0.45 M to about 0.75 M, about 0.45 M to about 0.7 M, about 0.45 M to about 0.65 M, about 0.45 M to about 0.6 M, about 0.45 M to about 0.55 M, about 0.45 M to about 0.5 M, about 0.5 M to about 0.85 M, about 0.5 M to about 0.8 M, about 0.5 M to about 0.75 M, about 0.5 M to about 0.7 M, about 0.5 M to about 0.65 M, about 0.5 M to about 0.6 M, about 0.5 M to about 0.55 M, about 0.55 M to about 0.85 M, about 0.55 M to about 0.8 M, about 0.55 M to about 0.75 M, about 0.55 M to about 0.7 M, about 0.55 M to about 0.65
M, about 0.55 M to about 0.6 M, about 0.6 M to about 0.85 M, about 0.6 M to about 0.8 M, about 0.6 M to about 0.75 M, about 0.6 M to about 0.7 M, about 0.6 M to about 0.65 M, about 0.65 M to about 0.85 M, about 0.65 M to about 0.8 M, about 0.65 M to about 0.75 M, about 0.65 M to about 0.7 M, about 0.7 M to about 0.85 M, about 0.7 M to about 0.8 M, about 0.7 M to about 0.75 M, about 0.75 M to about 0.85 M, about 0.75 M to about 0.8 M, about 0.8 M to about 0.85 M, or any ranges or values therebetween.
In addition to the recovery of electrode materials, the method disclosed herein may further comprise recovering current collectors, which may comprise copper, aluminium, nickel, titanium, platinum, zinc, stainless steel, carbonaceous materials, and carbon. Carbonaceous materials may comprise carbon-fibres, carbon wires and carbon cloth.
Besides the addition of surfactants, the method may further comprise agitating the solution. The agitation may comprise stirring, shaking, bubbling, recirculating or sonicating the solution.
Unlike the high temperatures required in the conventional pyrometallurgic methods, the method disclosed herein may not require heating or elevated temperatures and may be performed at room temperatures.
The temperature of the solution before agitation/sonication may be in a range of at least about 10 °C, at least about 15 °C, at least about 20 °C, at least about 23 °C, at least about 25 °C, at least about 30 °C, at least about 40 °C, at least about 50 °C; or from about 10 °C to about 50 °C, from about 10 °C to about 40 °C, from about 10 °C to about 30 °C, from about 10 °C to about 25 °C, from about 10 °C to about 23 °C, from about 10 °C to about 20 °C, from about 10 °C to about 15 °C, from about 15 °C to about 50 °C, from about 15 °C to about 40 °C, from about 15 °C to about 30 °C, from about 15 °C to about 25 °C, from about 15 °C to about 23 °C, from about 15 °C to about 20 °C, from about 20 °C to about 50 °C, from about 20 °C to about 40 °C, from about 20 °C to about 30 °C, from about 20 °C to about 25 °C, from about 20 °C to about 23 °C, from about 23 °C to about 50 °C, from about 23 °C to about 40 °C, from about 23 °C to about 30 °C, from about 23 °C to about 25 °C, from about 25 °C to about 50 °C, from about 25 °C to about 40 °C, from about 25 °C to about 30 °C, from about 30 °C to about 50 °C, from about 30 °C to about 40 °C, from about 40 °C to about 50 °C, or at most about 10 °C, or at most about 15 °C, or at most about 20 °C, or at most about 23 °C, at most about 25 °C, at most about 30 °C, at most about 40 °C, at most about 50 °C; or about 10 °C, about 15 °C, about 20 °C, about 23 °C, about 25 °C, about 30 °C, about 40 °C, about 50 °C, or any ranges or values therebetween. In a preferred embodiment, the sonication is performed with the temperature of the solution at 23 °C.
Agitation/sonication of solutions may cause a rise in temperature in liquids due to different processes such as adiabatic heating, molecular friction, energy dissipation within the liquid, and localized heating caused by cavitation. Hence, the rise in temperature of the solution after agitation/sonication is an expected phenomenon.
The temperature of the solution after agitation/sonication is at a range of at least about 10 °C, at least about 15 °C, at least about 20 °C, at least about 23 °C, at least about 25 °C, at least about 30 °C, at least about 40 °C, at least about 50 °C; least about 60 °C, at least about 70 °C, at least about 80 °C, at least about 90 °C; or from about 10 °C to about 90 °C, from about 10 °C to about 80 °C, from about 10 °C to about 70 °C, from about 10 °C to about 60 °C, from about 10 °C to about 50 °C, from about 10 °C to about 40 °C, from about 10 °C to about 30 °C, from about 10 °C to about 25 °C, from about 10 °C to about 23 °C, from about 10 °C to about 20 °C, from about 10 °C to about 15 °C, from about 15 °C to about 90 °C, from about 15 °C to about 80 °C, from about 15 °C to about 70 °C, from about 15 °C to about 60 °C, from about 15 °C to about 50 °C, from about 15 °C to about 40 °C, from about 15 °C to about 30 °C, from about 15 °C to about 25 °C, from about 15 °C to about 23 °C, from about 15 °C to about 20 °C, from about 20 °C to about 90 °C, from about 20 °C to about 80 °C, from about 20 °C to about 70 °C, from about 20 °C to about 60 °C, from about 20 °C to about 50 °C, from about 20 °C to about 40 °C, from about 20 °C to about 30 °C, from about 20 °C to about 25 °C, from about 20 °C to about 23 °C, from about 23 °C to about 90 °C, from about 23 °C to about 80 °C, from about 23 °C to about 70 °C, from about 23 °C to about 60 °C, from about 23 °C to about 50 °C, from about 23 °C to about 40 °C, from about 23 °C to about 30 °C, from about 23 °C to about 25 °C, from about 25 °C to about 90 °C, from about 25 °C to about 80 °C, from about 25 °C to about 70 °C, from about 25 °C to about 60 °C, from about 25 °C to about 50 °C, from about 25 °C to about 40 °C, from about 25 °C to about 30 °C, from about 30 °C to about 90 °C, from about 30 °C to about 80 °C, from about 30 °C to about 70 °C, from about 30 °C to about 60 °C, from about 30 °C to about 50 °C, from about 30 °C to about 40 °C, from about 40 °C to about 90 °C, from about 40 °C to about 80 °C, from about 40 °C to about 70 °C, from about 40 °C to about 60 °C, from about 40 °C to about 50 °C, from about 50 °C to about 90 °C, from about 50 °C to about 80 °C, from about 50 °C to about 70 °C, from about 50 °C to about 60 °C, from about 60 °C to about 90 °C, from about 60 °C to about 80 °C, from about 60 °C to about 70 °C, from about 70 °C to about 90 °C, from about 70 °C to about 80 °C, from about 80 °C to about 90 °C, or at most about 10 °C, or at most about 15 °C, or at most about 20 °C, or at most about 23 °C, at most about 25 °C, at most about 30 °C, at most about 40 °C, at most about 50 °C, at most about 60 °C, at most about 70 °C, at most about 80 °C, at most about 90 °C; or about 10 °C, about 15 °C, about 20 °C, about 23 °C, about 25 °C, about 30 °C, about 40 °C, about 50 °C, about 60 °C, about 70 °C, about 80 °C, about 90 °C, or any ranges or values therebetween.
Unlike the conventional use of strong acids which can cause leaching of metal ions into the acid solutions, the solution disclosed herein may not comprise metal ions leached from the batteries and/or capacitors. The solution may not contain dissolved metal ions from the batteries and/or capacitors and may remain in their original states without changes in their chemical compositions.
The present invention discloses a physical separation of the recovered electrode material from the current collectors without dissolution of metals, metal oxides, metal phosphates, metal silicates, mixed metal oxides, mixed metal phosphates and/or mixed metal silicates from the batteries and/or capacitors into the solution. The separation may be assisted by the presence of sulphates with the possible formation of hydrogen bonds between the anions, water molecules and the black mass (Fig. 20). The separation may also be further assisted by the presence of bubbles (cavitation) in the solutions shown in Fig. 20.
The present invention also discloses a battery or capacitor comprising the recovered electrode material disclosed herein.
The present invention also discloses an electrode material obtained by the method disclosed herein.
The recovered electrode material may be used in cathode and/or anode applications. For cathode applications, the recovered electrode material may be regenerated as a cathode by reacting with lithium precursors. For anode applications, the recovered electrode material may be used as an anode by mixing the recovered electrode materials with carbon and binders on metal foils.
The process of directly using recovered electrode material in new batteries/capacitors may allow for a sustainable approach towards battery /capacitor manufacturing, and the recovery and reintegration of the recovered electrode materials offer several advantages as follow below.
Firstly, the process helps reduce the environmental impact associated with battery production. By reusing electrode materials, the need for mining and extracting new resources is minimized, leading to a decrease in energy consumption and greenhouse gas emissions. Additionally, it helps mitigate the disposal of potentially hazardous materials from spent batteries, reducing the risk of soil and water contamination.
Secondly, utilizing recovered electrode materials promotes resource efficiency. Many battery components, such as lithium, cobalt, nickel, and other metals, are finite resources that are
costly to extract and refine. By recycling these materials from used batteries, valuable resources are conserved and can be reintroduced into the production cycle.
Once the recovered electrode materials are deemed suitable for reuse, they can be integrated into the manufacturing of new batteries. These materials may be combined with newly sourced components to create hybrid electrode structures, optimizing the performance and longevity of the battery cells. The reintegration of recovered materials may occur in various battery chemistries, including lithium-ion, nickel-metal hydride, or even emerging technologies like solid- state batteries.
The battery or capacitor comprising the recovered electrode material obtained from the method disclosed herein may have high galvanostatic charge and discharge capacities with stable electrochemical performance even after multiple cycles, showcasing that the present invention may offer great potential and advantages in reducing the environmental footprint and dependence on raw materials. This would allow for a more sustainable and circular approach within the battery /capacitor industry, supporting the transition towards a greener and more resource -efficient future.
Examples
Non-limiting examples of the invention will be further described in greater detail by reference to specific Examples, which should not be construed as in any way limiting the scope of the invention.
Example 1: Procedure for Preparing Solutions
Example la: Single Salt Sulphate-based Solutions
Example la(i): 0.5M Monovalent cationic (Li+/Na+/NH4+) sulphate solutions
0.1 mol of monovalent cationic sulphate salt (Li2SO4 or Na2SO4 or (NH4)2SO4) was dissolved in 0.2kg of DI water and stirred to ensure all the salts have been dissolved to form a homogenous 0.5M sulphate solution.
Example la(ii): 0.5M Divalent cationic (Mg2+/Zn2+) sulphate solutions
0.1 mol of divalent cationic sulphate salt (MgSC or ZnSO4) was dissolved in 0.2kg of DI water and stirred to ensure all the salts have been dissolved to form a homogenous 0.5M sulphate solution.
Example la(iii): 0.5M Trivalent cationic (Al3+) sulphate solution
0.1 mol of trivalent cationic sulphate salt (Ah SO^s) was dissolved in 0.6kg of DI water and stirred to ensure all the salts have been dissolved to form a homogenous 0.5M sulphate solution.
Example lb: Sulphate -based Solutions with Surfactant
Example lb(i): 0.5M Sodium dodecyl sulphate (SDS) solution [Table 1, Solution II
0.1 mol of SDS was dissolved in 0.2kg of DI water and stirred to ensure all the salts have been dissolved to form a homogenous 0.5M sulphate solution.
Example lb(ii): 0.5M Mixed (NH4)SO^ solution with SDS at 1:1 v/v [Table 1, Solution III
0.5M of the (NH4)2SO4 and SDS solutions prepared according to Example la(i) and la(iv) were mixed in equal volumes to form a homogenous 0.5M sulphate solution.
Example Ib(iii): 0.5M Mixed AllSo4 solution with SDS at 1:1 v/v [Table 1, Solution III1
0.5M of the Al(SO4)3 and SDS solutions prepared according to Example la(iii) and la(iv) were mixed in equal volumes to form a 0.5M homogenous sulphate solution.
Table 1. Sulphate-based solutions with sodium dodecyl sulphates (SDS)
Solution Formulation pH
I 0.5 mol kg 1 SDS in Di H2O ~6
II (0.5 mol kg 1 SDS in Di H2O) + ~5
(0.5 mol kg 1 (NH4)SCin Di H2O) at 1:1 v/v
III (0.5 mol kg 1 SDS in Di H2O) + ~4
(0.5 mol kg 1 A12(SC>4)3in Di H2O) at 1:1 v/v
Example 1c: Phosphate-based Solutions
0.5M Monovalent cationic (Li+/Na+/NH4+) phosphate solutions
0.1 mol of monovalent cationic phosphate salt (LilDPC^ or NaH2PO4 or (NH4)H2PO4 was dissolved in 0.2kg of DI water and stirred to ensure all the salts have been dissolved to form a homogenous 0.5M phosphate solution.
Example Id: Mixed Complex Salt Solutions
Example ld(i): Mixed monovalent cationic salt solution (NaCl + L1NO3+ NaNO3) [Table 2, Solution 11
0.1 mol of the individual monovalent cationic salt - NaCl, LiNO3, NaNO3 was separately dissolved in 0.2kg of DI water and stirred to ensure all the salts have been dissolved to form the respective homogenous 0.5M salt solutions. 0.5M of the respective NaCl, LiNO3, NaNO3 salt solutions were then mixed in equal volumes and stirred to ensure a homogenous mixed salt solution.
Example ld(ii): 0.5M mixed monovalent cationic sulphate solution (Li2SO4+ Na2SO4 + 2SO4) [Table 2, Solution 21
0.5M of the respective Li2SO4, Na2SO4, and (NH4)2SO4 salt solutions prepared according to Example la(i) were mixed in equal volumes and stirred to ensure a homogenous 0.5M sulphate solution.
Example Id(iii): 0.5M mixed ammonium and sodium dihydrogen phosphate solution (NaH PO4+ NH4H2PO4) [Table 2, Solution 31
0.1 mol of the individual monovalent cationic salt - NaPEPCC and NH4H2PO4 was separately dissolved in 0.2kg of DI water and stirred to ensure all the salts have been dissolved to form the respective homogenous 0.5M phosphate solutions. 0.5M of the respective NalEPCC and NH4H2PO4 phosphate solutions were then mixed in equal volumes and stirred to ensure a homogenous 0.5M phosphate solution.
Example ld(iv): Mixed salt solution containing sulphate and phosphate (Li SO4+ Na2SO4 + 2SO4 + NaH2PO4+ NH4H2PO4) [Table 2, Solution 41
0.5M of the respective salt solutions prepared according to Example ld(ii) and Id(iii) were mixed in equal volumes and stirred to ensure a homogenous mixed salt solution.
Example ld(v): Mixed salt solution containing sulphate (NaCl + LiNCh + NaNCh + Li2SO4+ Na?SO4 + [Table 2, Solution 51
0.5M of the respective salt solutions prepared according to Example ld(i) and ld(ii) were mixed in equal volumes and stirred to ensure a homogenous mixed salt solution.
Example ld(vi): Mixed salt solution containing phosphate (NaCl + L1NO3 + NaNO3 + NaH2PO4+
NH4H2PO4) [Table 2, Solution 61
0.5M of the respective salt solutions prepared according to Example ld(i) and Id(iii) were mixed in equal volumes and stirred to ensure a homogenous mixed salt solution.
Example Id(vii): Mixed salt solution containing sulphate and phosphate (NaCl + LiNO3 + NaNO3
0.5M of the respective salt solutions prepared according to Example 1 d(i)-(iii) were mixed in equal volumes and stirred to ensure a homogenous mixed salt solution.
Table 2. Mixed sulphates and/or phosphates in complex salt solutions
Solution Sulphate-, Sulphates-based Phosphates- Solution pH Remark phosphate- solution based solution mixture less solution ratio
Solution 1 (0.5M NaCl+ - - 1:0:0 5 Sulphate-, phosphate-less
0.5M LNO’, + (Control as a complex salt
0.5M NaNO’J solution) in DI water
Solution 2 - (0.5M Li2SO4+ - 0:1:0 5 Mixed sulphates-based
0.5M Na’SOr + solution
0.5M (NHO2SO4) in DI water
Solution 3 - - (0.5M Nal l’POr 0:0:1 4 Mixed phosphates-
•2H2O+ based solution
0.5M NH4H2PO4) in DI water
Solution 4 - Solution 2 Solution s 0:1:1 4 Mixed sulphates and phosphates-based solution
Solution 5 Solution 1 Solution 2 - 1:1:0 5 A mixture of complex salt solution and sulphates- based solution
Solution 6 Solution 1 - Solution s 1:0:1 4 A mixture of complex salt solution and phosphates- based solution
Solution 7 Solution 1 Solution 2 Solution s 1: 1:1 4 A mixture of complex salt solution, sulphates and
Example 2: Characterization of Solutions
Example 2a: Raman Spectroscopy of Single Salt Sulphate-based Solutions
The dominant Raman bands corresponding to the different components of the solution were labelled “X”, “Y” and “Z”. The Raman band region labelled Xa corresponds to the different monovalent and multivalent cations -based sulphates components while the Raman band regions labelled Yi and Y2 correspond to the DI H2O component.
Example 2a(i): Raman Spectra of Monovalent cationic (Li+/Na+/NH4+) sulphate solutions (Example la(i))
The presence of a peak in the band region labelled Xa in the Raman spectra of lithium, sodium, and ammonium sulphate solutions (Fig. 4) indicated the presence the different monovalent cations-based (Li+/Na+/NH4+) sulphates components absent in DI water. The presence of the peaks in the Raman band regions labelled Y 1 and Y2 indicated the presence of the DI H2O component.
Example 2a(ii): Raman Spectra of Divalent cationic (Mg2+/Zn2+) sulphate solutions (Example la(iil)
The presence of a peak in the band region labelled Xa in the Raman spectra of magnesium and zinc sulphate solutions (Fig. 4) indicated the presence the different divalent cations-based (Mg2+/Zn2+) sulphates components absent in DI water. The presence of the peaks in the Raman band regions labelled Yi and Y2 indicated the presence of the DI H2O component.
Example 2a(iii): Raman Spectrum of Trivalent cationic (Al3+) sulphate solutions (Example la(iii))
The presence of a peak in the band region labelled Xa in the Raman spectra of aluminium sulphate solutions (Fig. 4) indicated the presence the trivalent cation-based (Al3+) sulphate component absent in DI water. The presence of the peaks in the Raman band regions labelled Y 1 and Y2 indicated the presence of the DI H2O component.
Example 2b: Raman Spectroscopy of Sulphate-based Solutions with Surfactant
The mixed (NH4)SCC solution with SDS at 1:1 v/v of Example lb(ii) was identified through the distinct Raman bands of SDS appearing in the regions labelled “Zi” and “Z2” (Fig. 5a), together with the Raman bands in regions “Xa”, “Yi” and “Y2”.
Example 2b(ii): Raman Spectrum of Mixed Al2SOb) solution with SDS at 1:1 v/v (Example Ib(iii))
The mixed A^SCbb solution with SDS at 1:1 v/v of Example la(vi) was identified through the distinct Raman bands of SDS appearing in the regions labelled “Zi” and “Z2” (Fig. 5b), together with the Raman bands in regions “Xa”, “Yi” and “Y2”.
Example 2b(iii): Raman Spectrum of powdered SDS
The characteristic Raman bands of the SDS surfactant were identified through the distinct peaks appearing in the regions labelled “Zi” and “Z2” in the Raman spectrum (Figs. 5a-5b).
Example 2c: Raman Spectroscopy of Phosphate -based Solutions
Example 2c(i): Raman Spectra of ammonium sulphate versus ammonium phosphate solution
The differences between ammonium phosphate and ammonium sulphate solutions were indicated with the distinct Raman band positions and intensity differences, with the absence of peaks Xa and the presence of peaks Xb for the ammonium phosphate solution (Fig. 6).
Example 2d: Raman Spectroscopy of Mixed Complex Salt Solutions
Example 2d(i): Raman Spectrum of mixed monovalent cationic salt solution (NaCl + LiN03+ NaNO3) (Example ld(i))
The mixed (NaCl + LiN03+ NaNO3) cationic salt control solution of Example 1 d(i) was identified through the distinct Raman bands as a control solution (Fig 7(a)).
Example 2d(ii): Raman Spectrum of mixed monovalent cationic sulphate solution (L12SO4+ Na?SO4 + (NH4)2SO4) (Example ld(ii))
A control solution with sulphate-based solution with Example ld(ii) was identified through the Raman bands which consists of Raman bands of the control solution as well as the other Raman bands corresponding to the sulphate-based solution (Fig. 7(b)).
Example 2d(iii): Raman Spectra of ammonium and sodium dihydrogen phosphate solution (NaH2PO4+ NH4H2PO4) (Example Id(iii))
A control solution with phosphate-based solution with Example Id(iii) was identified through the Raman bands which consist of Raman bands of the control solution as well as the other Raman bands corresponding to the phosphate-based solution (Fig. 7(c)).
Example 2d(iv): Raman Spectra of mixed complex salt solution containing sulphate and phosphate (NaCl + LiNO3 + NaNO3 + Li2SO4+ Na2SO4 + (NH4)2SO4 + NaH2PO4+ NH4H2PO4) (Example Id(vii))
A control solution with sulphate-based and phosphate-based solution with Example ld(iv) was identified through the Raman bands which consist of Raman bands of the control solution as well as the other Raman bands corresponding to the sulphate- and phosphate-based solutions (Fig. 7(d)).
Example 2e: Raman Spectroscopy of Rainwater
Example 2e: Raman Spectrum of Rainwater
Confocal Raman spectroscopy results indicated that the peaks in the Raman band regions labelled Yi and Y2 in rainwater (Fig. 8(a)) were found to be similar to the peaks in the Raman band of DI H2O (Fig. 8(b)), suggesting that rainwater and DI H20 have similar solution structures.
Example 2f: Anion Chromatography technique
Ion chromatography technique using Dionex ICS- 1000 Anion was employed to determine the anion species in rainwater. The concentration of anions was referenced with Dionex Seven Anion Standard Combined Standard Solution. The results indicated that the concentration of NO3 and SO4 2 were the dominant anion species in rainwater (Fig. 9). Anions such as fluorides and phosphates are not detected in the collected local rainwater sample.
Example 2g: pH of Solutions
Using DI water and rainwater as control solutions, the formulated 0.5M sulphate-based solutions comprising Li, Na, NH4, Mg, Zn and Al cations in Example 1 were measured using pH- indicator strips and were found to be between pH 4 to 7 (Fig. 3). Di-water and rainwater were found to have a pH value of ~4. Li- and Zn- based sulphates solutions were found to have a pH value of ~5. Na-, NH4-, Mg- based sulphates solutions were found to have a pH value of ~6. Al- based sulphate solution was found to have a pH value of ~4.
Example 3: Method of Recovering Electrode Materials from Batteries/Capacitors
Example 3a: Shredding of batteries/capacitors
Spent batteries were placed into a shredder where the batteries/capacitors were physically shredded and the internal components such as electrode materials and current collectors were exposed (Fig. 1(b)).
Example 3b: Sonication and Separation
The shredded batteries/capacitors are then immersed in the solutions of Example 1 and sonicated to facilitate dislodgement/delamination of the electrode materials from the current collectors. A sieve system may be employed to facilitate the separation (Fig. 2). The sieve system consists of two containers, with a primary (inner) container having two rows of designated placement of 3 mm holes that functions as a sieve while the outer container functions as a secondary containment container (Fig. 2(a)). The containers containing the shredded battery/capacitor materials and solutions were then sonicated to dislodge/delaminate the electrode materials from the current collectors. The sonication process assists in the separation of the separated finer electrode materials from the larger current collectors, allowing the separated electrode materials to pass through the holes into the secondary . The current collectors were then collected directly from in the primary (inner) container. The separation of the recovered electrode materials and the current collectors was achieved by the simple and straightforward removal of the primary container from the secondary container.
Example 3c: Centrifugation and Drying
The separated electrode materials suspended in the solution in Example 3b were then recovered by further centrifugation and drying processes.
Example 3d: Recycling of Solution
The solutions recovered in Example 3c may then be reused for a next batch of recovery as described in Examples 3b and 3c.
Example 4: Performance of Different Solutions
Example 4a: Rainwater
Rainwater was presented as an effective solution as compared to DI H2O (Fig. 10) to dislodge/ delaminate the electrode materials from the current collectors, despite both having similar solution structure based on confocal Raman spectroscopy results (Fig. 8). It was suggested that the presence of ions in the rainwater might be the key contribution factor for an ideal recycling solution. As the rainwater were known to contain nitric, sulphuric and hydrochloric acids, diluted H2SO4 and HNO3 (Fig. 10) were prepared as control samples for comparison purposes. It was noteworthy that despite the close pH readings of prepared H2SO4 (pH 2.56) and HNO3 (pH 2.83) solutions, the diluted H2SO4 solution was able to remove the electrode materials into the solution better than the diluted HNO3 solution after the sonication process. On the other hand, rainwater while having a much milder pH ~4-5 than that of diluted H2SO4 solution, demonstrated good efficiency in the removal of the electrode materials from the current collectors, highlighting the importance of sulphate anions as a critical component for an ideal recycling solution.
Example 4b: Sulphate -based Solutions
While the electrode sonicated in the DI H2O had the electrode materials remained largely intact and unseparated on the current collector (Fig. 11), in stark contrast, the electrode materials sonicated in sulphates-containing solution (e.g., rainwater or monovalent/multivalent cations - based, had the majority of their electrode materials dislodged/ delaminated from the aluminium current collector after 2 and 5 minutes of sonication at 25 °C respectively in Fig. 11.
Example 4c: Phosphate-based Solutions
The feasibility of employing phosphates -based solution for direct recycling purposes was demonstrated by preparing NH4+-based phosphates and sulphates -based solutions according to Examples la(i) and lc(i). Similar to the effectiveness of sulphate-based solution, the phosphate- based solution was also found to be capable of delaminating/dislodging the electrode materials effectively from the copper current collector (Fig. 12).
Example 4d: Sulphate-based Solutions with sodium dodecyl sulphate (SDS)
Although the sulphates -based recycling solution was found to be effective in delaminating/dislodging the electrode materials during the sonication process, it was noted that the aluminium current collector recovered using NHA and Al3+ suffered from severe breakage and corrosion (Fig. 11). The breakage and corrosion were likely to be caused by the interaction between the dissolved ions and the collector during the sonication process. Such reaction resulted in additional filtration and extraction steps to separate the dislodged/delaminated active materials and broken foil pieces, and a poorer quality of the recovered Al current collector. Sodium dodecyl sulphate (SDS) was then added into the recycling solutions to overcome the issues with breakage and corrosion of the current collector.
The composite salt-based solutions based on NHA and Al3+ sulphates with SDS were formulated according to Table 1 (Solution II and III respectively) and in Example lb(ii)-(iii). The single salt solution based on SDS in DI H2O was prepared as a control solution (Solution I) and according to Example lb(i). As shown in Fig. 13, the electrode materials were completely removed without the breakage and corrosion of the aluminium current collector after the electrodes were sonicated in solution with SDS. On the other hand, the electrode sonicated in the control solution (Solution I) had the bulk of electrode materials intact on the aluminium collector, demonstrating the importance of composite salt-based solution for effective removal of the electrode materials from the current collector without any damage to the current collector.
Example 4e: Mixed Sulphate and/or Phosphate -based Solutions
A series of solutions (Solution 1 to 7) was prepared according to Table 2 to evaluate the effect of mixed sulphates and/or phosphates -based solution in a complex solution environment (e.g., in a mixed cations and anions environment) for the delamination of electrodes. The electrodes were placed into the respective solutions 1 to 7 in Fig. 14. Solution 1 was set as the control solution with no sulphates and phosphates anions present. The electrodes were then sonicated in the prepared solutions, with the results taken after a duration of 1 minute and 15 minutes respectively. Distinctively, in the presence of mixed sulphates and phosphates -based solution, the electrodes were effectively delaminated off the aluminium current collector as compared to the electrode in the control solution after 15 minutes (Fig. 14). Furthermore, no corrosion of the recovered aluminium foil (current collector) was observed when sonicated in the solution with mixed sulphates and/or phosphate system.
Example 5: Recovered Electrode Materials
Example 5a: Characterization
The elemental composition and crystal structure of the recovered electrode materials were characterized using a scanning electron microscope (SEM) coupled with electron dispersive X-ray spectrometer (EDS) (JEOL FESEM 7600F) and X-ray diffractometer (Bruker D8 Advance), respectively. Match! software was used to analyze the X-ray diffraction pattern based on inorganic crystal structure database (ICSD). Based on the SEM -EDS measurement, the elemental compositions of Ni, Co, Al, O, and C were detected (Fig. 15). From the X-ray diffraction pattern of the recycled materials, a composite of lithium cobalt nickel aluminium oxides and carbon-based materials (carbon and graphite) were identified (Fig. 16).
Example 5b: Application of Recovered Electrode Materials
The feasibility of the recovered materials was tested for anode applications. Prototypes in the form of a coin cell were assembled and electrochemically tested. A slurry was prepared by mixing the recycled materials with conductive carbon black and polyvinylidene fluoride (PVDF) binder in a weight ratio of 8: 1 : 1. The slurry was then cast onto a copper foil using a doctor blade, followed by the overnight vacuum drying process. A half-cell configuration (Fig. 17) was assembled to test the electrode (active mass~2 mg) as the anode (working electrode) with 16 mm lithium foil as counter and reference electrode. A monolayer polypropylene (Celgard 2400) was employed as a separator while the 1 M LiPFe in ethylene carbonate (EC): ethyl methyl carbonate (EMC) 3:7 v/v was used as the electrolyte. The coin cell was then assembled in a glovebox under an inert argon environment. The half-cell was electrochemically cycled between the range of 0.005 V to 2.5 V at a current density of 300 mA g \ with a rest time of 1 minute in between steps.
The galvanostatic charge and discharge curves of the recovered materials/Li cell are shown in Fig. 18. Remarkably, the direct application of recovered electrode materials as the anode delivered a high discharge capacity of 446.4 mAh g 1 in the initial cycle at a current density of 300 mA g-1. Moreover, the cell also exhibited a stable electrochemical performance with a discharge capacity of -138.1 mAh g 1 after 100 cycles (Fig. 19).
Industrial Applicability
The present invention relates to a method of recovering electrode material from a battery or a capacitor, wherein an electrode of the battery or capacitor is exposed to a solution comprising sulphate, phosphate, nitrate and/or chloride ions. The solution in the method disclosed herein is environmentally friendly and non-hazardous, which obviates the need for conventional strong acids used in leaching or high energy input for pyrometallurgical means, and may not require extensive post-treatment steps to recover electrode materials . Furthermore, the disclosed method of recovering electrode material from a battery or a capacitor may be cost-effective, simple, environmentally friendly, and scalable in the manufacturing process for mass production.
It will be apparent that various other modifications and adaptations of the invention will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the spirit and scope of the invention and it is intended that all such modifications and adaptations come within the scope of the appended claims.
Claims
CLAIMS A method of recovering electrode material from a battery or capacitor, wherein an electrode of the battery or capacitor is exposed to a solution comprising sulphate, phosphate, nitrate and/or chloride ions. The method of claim 1, wherein the electrode material comprises metal oxides, metal phosphates, metal silicates, mixed metal oxides, mixed metal phosphates, mixed metal silicates, elemental silicon, silicon oxides, carbonaceous materials, carbon, hydrocarbons and/or polymers. The method of claim 2, wherein the metal or mixed metal is selected from the group consisting of lithium, cobalt, nickel, aluminium, manganese, chromium, iron, titanium, and combinations thereof. The method of any one of claims 1 to 3, wherein the electrode material is selected from the group consisting of lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium titanium oxide, lithium nickel oxide, lithium manganese dioxide, lithium manganese nickel oxide, lithium nickel cobalt aluminium oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium manganese phosphate, lithium nickel phosphate, lithium cobalt phosphate and lithium manganese silicate. The method of any one of claims 1 to 4, wherein the pH of the solution is in the range of about 4 to about 7. The method of any one of claims 1 to 5, wherein the solution comprises metal salts and/or ammonium salts of sulphate, phosphate, nitrate and/or chloride. The method of claim 6, wherein the metal of the metal salt is selected from the group consisting of lithium, sodium, magnesium, zinc, and aluminium. The method of any one of claims 1 to 7, wherein the solution is selected from the group selected consisting of:
(i) solution comprising sulphate ions;
(ii) solution comprising phosphate ions;
(iii) solution comprising sulphate and phosphate ions;
(iv) solution comprising chloride, nitrate and sulphate ions;
(v) solution comprising chloride, nitrate, and phosphate ions; and
(vi) solution comprising chloride, nitrate, sulphate, and phosphate ions.
The method of any one of claims 1 to 8, wherein the solution is selected from the group consisting of:
(i) solution comprising sulphate ions;
(ii) solution comprising phosphate ions;
(iii) solution comprising sulphate and phosphate ions in a ratio of about 2:8 to about 8:2;
(iv) solution A comprising chloride and nitrate ions, and solution B comprising sulphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B is in the range of about 2:8 to about 8:2;
(v) solution A comprising chloride and nitrate ions, and solution C comprising phosphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution C is in the range of about 2:8 to about 8:2; and
(vi) solution A comprising chloride and nitrate ions, solution B comprising sulphate, and solution C comprising phosphate, wherein the ratio of chloride to nitrate is in the range of about 2:8 to about 8:2, and the ratio of solution A to solution B to solution C is in the range of about (2 to 4):(2 to 4):(2 to 4). The method of any one of claims 1 to 9, wherein the solution is selected from the group selected consisting of:
(i) solution comprising sulphate ions;
(ii) solution comprising phosphate ions;
(iii) solution comprising sulphate and phosphate ions in a ratio of about 1:1;
(iv) solution A comprising chloride and nitrate ions, and solution B comprising sulphate, wherein the ratio of chloride to nitrate is in the range of about 1:1;
(v) solution A comprising chloride and nitrate ions, and solution C comprising phosphate, wherein the ratio of chloride to nitrate is in the range of about 1:1, and the ratio of solution A to solution C is in the range of about 1:1; and
(vi) solution A comprising chloride and nitrate ions, solution B comprising sulphate, and solution C comprising phosphate, wherein the ratio of chloride to nitrate is in the range of about 1:1, and the ratio of solution A to solution B to solution C is in the range of about 1:1:1. The method of any one of claims 1 to 10, wherein the concentration of sulphate, phosphate, nitrate and/or chloride ions is about 0.3 M to about 2 M. The method of any one of claims 1 to 11, wherein the solution further comprises a sulphate - containing surfactant. The method of claim 12, wherein the surfactant is selected from a group consisting of ammonium lauryl sulphate, sodium laureth sulphate, sodium myreth sulphate, sodium pareth sulphate, ammonium laureth sulphate, sodium lauryl sulphate, and sodium dodecyl sulphate (SDS).
The method of claims 12 or 13, wherein the concentration of sulphate ions in surfactant is about 0.01 M to about 0.85 M. The method of any one of claims 1 to 14, wherein the method further comprises recovering current collector. The method of any one of claims 1 to 15, wherein the current collector comprises copper, aluminium, nickel, titanium, stainless steel, carbonaceous materials, and carbon. The method of any one of claims 1 to 16, wherein the method further comprises agitating the solution. The method of claim 17, wherein the temperature of the solution before agitation is about 20 °C to about 40 °C. The method of claim 17, wherein the temperature of the solution during and/or after agitation is about 20 °C to about 80 °C. The method of any one of claims 1 to 19, wherein the solution does not comprise metal ions leached from the batteries and/or capacitors. A battery or capacitor comprising the recovered electrode material of any one of claims 1 to 20. Electrode material obtained by the method of any one of claims 1-20.
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